CN1584631A - Dye-containing resist composition and color filter using same - Google Patents

Dye-containing resist composition and color filter using same Download PDF

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Publication number
CN1584631A
CN1584631A CNA200410057004XA CN200410057004A CN1584631A CN 1584631 A CN1584631 A CN 1584631A CN A200410057004X A CNA200410057004X A CN A200410057004XA CN 200410057004 A CN200410057004 A CN 200410057004A CN 1584631 A CN1584631 A CN 1584631A
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Prior art keywords
compound
dyestuff
resist composition
methyl
solvent
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CNA200410057004XA
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CN1584631B (en
Inventor
保坂和义
周藤真理子
铃木正睦
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The invention presents: a dye-containing resist composition containing a ketol solvent; a negative resist composition containing a resin, a photo-acid generating agent or photo-base generating agent, a crosslinking compound, a dye and a ketol solvent; a negative resist composition containing a resin, a photo-radical generating agent, a crosslinking compound, a dye and a ketol solvent; a positive resist composition containing a resin, a photo-acid generating agent, a crosslinking compound, a dye and a ketol solvent; a resist composition containing [beta]-hydroxyketone as the ketol; and a resist composition containing 4-hydroxy-4-methyl-2-pentanone as the ketol.

Description

Contain the resist composition of dyestuff and the color filter that uses it
Technical field
The present invention relates to contain the resist composition of dyestuff and the color filter that uses it.
Background technology
The color filter that imaging apparatus such as solid-state imager or liquid crystal display cells is used, thus high meticulous color filter can be made owing to can form fine pattern, and therefore main employing forms method of patterning by the photoresist that has added pigment and makes.Use the resist composition contain pigment and macromolecule resin in the method, it is coated on the substrate after the film forming, adopt photoetching process to make dyed layer form pattern, form a colored pattern by developing, every kind of color repeats this operation, makes color filter.
At this moment, in the pigment that uses as colorant, generally use the good pigment of thermotolerance and photostability, and proposed to make the resist of pigment dispersing.For example disclose the photosensitive color resin combination, be characterised in that contain can be by resinous material, photoacid generator and the pigment of acid cure.Wherein disclosing resinous material is to contain the resin of phenol and the crosslinking chemical with N-methylol structure.(for example, patent documentation 1)
Yet because pigment itself contains the particle about 1 μ m, its particle exerts an influence, thereby can not form fine pattern.Therefore require the making of the color filter of high-resolution charge bonded element (CCD) usefulness to become difficult.
In contrast, using under the situation of dyestuff as pigment,, therefore can obtain uniform resist composition, therefore, and making the resist composition of pigment dispersing compare, can form fine pattern because dyestuff is solvable with respect to organic solvent.The negative resist composition of the resin, crosslinking chemical, photoacid generator, dyestuff and the solvent that contain by acid cure for example, is disclosed.As above-mentioned solvent, illustration has methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, glycol monomethyl isopropyl ether, propylene glycol monomethyl ether, N,N-dimethylacetamide, N-Methyl pyrrolidone, gamma-butyrolacton, cyclohexanone, ethyl acetate, n-butyl acetate, acetic acid propylene glycol list ethylether, methyl lactate, ethyl lactate, ethyl pyruvate, dimethyl formamide etc.(for example, patent documentation 2).
[patent documentation 1] spy opens flat 4-163552 communique
[patent documentation 2] spy opens flat 6-51514 communique
Summary of the invention
Generally the dissolubility in organic solvent is low owing to dyestuff, therefore is difficult to improve the dye strength in the resist composition.Particularly under the situation that the color filter filming is further made progress,, be necessary to improve the dye strength in the resist composition in order to show the spectrophotometric spectra of regulation.In addition, under the low situation of dyestuff and resin intermiscibility, when using dyestuff, resin and organic solvent modulation resist composition, exist dyestuff not dissolve or separate out, also have dyestuff precipitation, the crystallization more easily that dissolubility is low in organic solvent when preserving the resist composition, and be easy to generate problem such as foreign matter.
The present invention is in order to adapt to the filming of color filter, improves coloured resist composition that dye strength can not produce problem such as foreign matter yet even provide.
The 1st viewpoint of the present invention is the resist composition that contains dyestuff that contains the ketols solvent.
The 2nd viewpoint is the negative resist composition that contains resin (a-1), photoacid generator or Photobase generator (b-1), cross-linked compound (c-1), dyestuff (d) and ketols solvent (e).
The 3rd viewpoint is the negative resist composition that contains resin (a-2), optical free radical propellant (b-2), cross-linked compound (c-2), dyestuff (d) and ketols solvent (e).
The 4th viewpoint is the negative resist composition that contains resin (a-3), photoacid generator (b-3), cross-linked compound (c-3), dyestuff (d) and ketols solvent (e).
The 5th viewpoint is the resist composition that the 1st viewpoint to the 4 viewpoints are put down in writing in each, and solvent is the solvent that contains at least 1 weight % keto-alcohol with respect to whole solvent.
The 6th viewpoint is the resist composition that the 1st viewpoint to the 5 viewpoints are put down in writing in each, and keto-alcohol is a beta-hydroxy ketone.
The 7th viewpoint is the resist composition that the 1st viewpoint to the 5 viewpoints are put down in writing in each, and keto-alcohol is 4-hydroxy-4-methyl-2 pentanone.
The 8th viewpoint is a manufacturing method of color filter, comprises that the resist composition that the 1st viewpoint to the 7 viewpoints are put down in writing in each is coated on the substrate, dry, operation that exposure is developed then.
The 9th viewpoint is to adopt the color filter of the method manufacturing of putting down in writing in the 8th viewpoint.
The 10th viewpoint is the solid-state imager with the color filter that adopts the method manufacturing of putting down in writing in the 8th viewpoint.
The 11st viewpoint is the liquid crystal display cells with the color filter that adopts the method manufacturing of putting down in writing in the 8th viewpoint.
And the 12nd viewpoint is the diode displaying element with the color filter that adopts the method manufacturing of putting down in writing in the 8th viewpoint.
The present invention is in order to adapt to the filming of color filter, even improve dye strength and also can guarantee also not follow dye precipitated under the dissolubility long preservation of sufficient dyestuff and produce problem such as foreign matter, coloured resist composition that storage stability is high even provide, tested use ketols solvent as solvent, preferred beta-hydroxy ketone, preferred especially 4-hydroxy-4-methyl-2 pentanone.
Keto-alcohol is also referred to as hydroxy-ketone, is the general name that contains the ketone of hydroxyl.Preferred especially beta-hydroxy ketone in the keto-alcohol.This is because the carbonyl of interior hydroxyl of molecule and ketone is positioned at the interaction raising of certain location relation (β position) and dye molecule, and dissolubility increases, even also can not follow the precipitation of dyestuff composition and produce foreign matter etc. for temperature variation and long the preservation.Particularly 4-hydroxy-4-methyl-2 pentanone is the most excellent aspect these effects in the beta-hydroxy ketone.
As a result, the intermiscibility of the dissolubility of dyestuff and dyestuff and resin improves, and can guarantee the dye strength stipulated, therefore can make the color filter that can show desired spectrophotometric spectra.
The present invention is by in being carried out the negative resist composition that contains dyestuff or eurymeric resist composition that crosslinked, polymerization or depolymerization form by heat or rayed, contain the ketols solvent, preferred beta-hydroxy ketone, preferred especially 4-hydroxy-4-methyl-2 pentanone, the dissolubility of dyestuff and the intermiscibility of dyestuff and resin can be improved, and the dye strength stipulated can be guaranteed.The result can make the color filter that can show the regulation spectrophotometric spectra, and can use these color filters to make solid-state imager, liquid crystal display cells and diode displaying element.Also have by containing 4-hydroxy-4-methyl-2 pentanone, can be suppressed at production of foreign matters when preserving the resist composition.
Embodiment
The present invention is the resist composition that contains the dyestuff that comprises the ketols solvent.
More particularly, resist composition of the present invention goes for minus and eurymeric.
As the negative resist composition, the firstth, contain the negative resist composition of resin (a-1), photoacid generator or Photobase generator (b-1), cross-linked compound (c-1), dyestuff (d) and ketols solvent (e), the secondth, contain the negative resist composition of resin (a-2), optical free radical propellant (b-2), cross-linked compound (c-2), dyestuff (d) and ketols solvent (e).
In addition, as eurymeric resist composition, be the eurymeric resist composition that contains resin (a-3), photoacid generator (b-3), cross-linked compound (c-3), dyestuff (d) and ketols solvent (e).
The resin that uses in the negative resist composition is the resin (a-1) that solidifies by acid that is produced by heat or rayed or alkali, by heat or the crosslinked photoresist (a-2) of rayed, as long as filming of unexposed portion can be removed by developer solution in this resin, then there is no particular limitation.
As resin (a-1), specifiable is resin of for example containing hydroxyl or carboxyl etc.
For example specifiablely be polyvinyl alcohol (PVA), polyacrylamide, acrylic resin such as polyacrylic acid and polymethylacrylic acid, polyamic acid, polycarboxylated styrene, the polycarboxylated styrene derivant, the multipolymer of polymethacrylate and maleic anhydride, phenolics, novolac resin, the polyimide that contains hydroxyl and/or carboxyl, cellulose, cellulose derivative, starch, chitin, chitosan, gelatin, zein, sugar skeleton macromolecular compound, polyamide, polyethylene terephthalate, polycarbonate, polyurethane and polysiloxane.These resins can separately or make up 2 kinds or its above use.
Particularly preferably be polycarboxylated styrene, polycarboxylated styrene derivant, phenolics and novolac resin.
As the acrylic resin that contains carboxyl, specifiable is to be principal ingredient with (methyl) acrylate, copolymerization the acrylic copolymers that obtain of ethene unsaturated carboxylic acid and other monomers as required etc.
As (methyl) acrylate, specifiable is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid dimethylamino ester, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) glycidyl acrylate.
As the ethene unsaturated carboxylic acid, can use acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, furoate clothing and their acid anhydrides and half ester.Wherein preferred acrylic acid, methacrylic acid, maleic acid.
The weight-average molecular weight of aforesaid propylene acid copolymer is 1000～100,000, is preferably 2000～30,000 from development, fusible viewpoint.These can make up as required, both can use separately, also can make up 2 kinds or its above use.
As polycarboxylated styrene and polycarboxylated styrene derivant, the multipolymer that has homopolymer, vinylphenol and other compound copolymerization of vinylphenol to obtain.As other compounds at this moment, specifiable be acrylic acid derivative, vinyl cyanide, methacrylic acid derivative, methacrylonitrile, styrene, α-Jia Jibenyixi, p-methylstyrene, o-methyl styrene, to methoxy styrene, to styrene derivatives such as chlorostyrenes.
The weight-average molecular weight of above-mentioned polycarboxylated styrene and polycarboxylated styrene derivant is 1000～100,000, is preferably 2000～30,000 from development, fusible viewpoint.These can make up as required, both can use separately, also can make up 2 kinds or its above use.
As novolac resin, specifiable is oxybenzene compound and aldehyde compound or the ketonic compound material that condensation obtains in the presence of acid catalyst.
As oxybenzene compound, specifiable is phenol, metacresol, paracresol, orthoresol, m-ethylphenol, paraethyl phenol, o-ethyl phenol, 2,3, the 5-pseudocuminol, 2,3,5-triethyl phenol, the 4-tert-butyl phenol, the 3-tert-butyl phenol, the 2-tert-butyl phenol, the 2-tert-butyl group-4-methylphenol, the 2-tert-butyl group-5-methylphenol, p methoxy phenol, meta-methoxy phenol, to thanatol, m-oxethyl phenol, to propoxyl group phenol, between propoxyl group phenol, adjacent isopropenyl phenol, to isopropenyl phenol, 2-methyl-4-isopropenyl phenol, 2-ethyl-4-isopropenyl phenol, 2, the 3-xylenols, 2, the 5-xylenols, 3, the 5-xylenols, 3, the 4-xylenols, resorcinol, quinhydrones, 4, the 4-dihydroxybiphenyl, phenylphenol, catechol, 1,2,3,-thrihydroxy-benzene, naphthols, bisphenol-c, bisphenol-A etc.These oxybenzene compounds can separately or make up 2 kinds or its above use.
As aldehyde compound, specifiable is formaldehyde, paraformaldehyde, acetaldehyde, trioxane, propionic aldehyde, butyraldehyde, trimethyl-acetaldehyde, acryl aldehyde, crotonaldehyde, hexamethylene aldehyde, furfural, furylacrolein, benzaldehyde, terephthalic aldehyde, phenyl acetaldehyde, α-hydrocinnamicaldehyde, beta-phenyl propionic aldehyde, salicylaldhyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, o-methyl-benzene formaldehyde, a tolyl aldehyde, p-tolyl aldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, 4-chloro-benzaldehyde, cinnamic acid etc.These aldehyde compounds can separately or make up 2 kinds or its above use.
As ketonic compound, specifiable is acetone, MEK, diethyl ketone, benzophenone etc.These ketonic compounds can separately or make up 2 kinds or its above use.
The acid catalyst that uses during as condensation reaction, specifiable is hydrochloric acid, sulfuric acid, formic acid, ethane diacid, p-toluenesulfonic acid etc.
The weight-average molecular weight of above-mentioned novolac resin is 1000～100,000, is preferably 2000～30,000 from development, fusible viewpoint.These can make up as required, both can use separately, also can make up 2 kinds or its above use.
Resin (a-2) as containing by the crosslinked photonasty group of heat or rayed can use the acrylic resin that contains carboxyl.Be principal ingredient promptly with (methyl) acrylate, copolymerization the acrylic copolymers that obtain of ethene unsaturated carboxylic acid and other monomers as required.
As (methyl) acrylate, specifiable is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid dimethylamino ester, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) glycidyl acrylate.
As the ethene unsaturated carboxylic acid, can use acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, furoate clothing and their acid anhydrides and half ester.Wherein preferred acrylic acid, methacrylic acid, maleic acid.
As other monomers, specifiable is acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile, styrene, α-Jia Jibenyixi, vinyl acetate, alkyl vinyl ether etc.
The weight-average molecular weight of aforesaid propylene acid copolymer is 1000～100,000, is preferably 2000～30,000 from development, fusible viewpoint.These can make up as required, both can use separately, also can make up 2 kinds or its above use.
In the light trigger (b-1) that when using resin (a-1), uses, as photoacid generator, so long as promptly do not limit especially by the direct or indirect acidic material of rayed.Can use compound in triazine class, acetophenone derivs compound, two sulfone compounds, diazomethane compounds, sulfonic acid compound, diaryl group iodized salt, triarylsulfonium salt, San Fang Ji phosphonium salt, iron arene complex compound etc. as object lesson, but be not limited to these.Concrete specifiable for example is, the diphenyl lodine chloride, the trifluoromethanesulfonic acid diphenyl iodnium, the methane-sulforic acid diphenyl iodnium, the diphenyl IBr, the tetrafluoro boric acid diphenyl iodnium, the hexafluoro-antimonic acid diphenyl iodnium, the hexafluoroarsenate diphenyl iodnium, hexafluorophosphoric acid two (to tert-butyl-phenyl) salt compounded of iodine, methane-sulforic acid two (to tert-butyl-phenyl) salt compounded of iodine, toluenesulfonic acid two (to tert-butyl-phenyl) salt compounded of iodine, trifluoromethanesulfonic acid two (to tert-butyl-phenyl) salt compounded of iodine, tetrafluoro boric acid two (to tert-butyl-phenyl) salt compounded of iodine, two (to tert-butyl-phenyl) lodine chloride, two (rubigan) lodine chloride, tetrafluoro boric acid two (rubigan) salt compounded of iodine, triphenyl chlorination sulfonium, triphenyl bromination sulfonium, tetrafluoro boric acid three (p-methoxyphenyl) sulfonium, hexafluorophosphoric acid three (p-methoxyphenyl) sulfonium, tetrafluoro boric acid three (to ethoxyl phenenyl) sulfonium, triphenyl phosphonium chloride, the triphenyl phosphonium bromide, tetrafluoro boric acid three (p-methoxyphenyl) Phosphonium, hexafluorophosphoric acid three (p-methoxyphenyl) Phosphonium, tetrafluoro boric acid three is (to ethoxyl phenenyl) Phosphonium.
Also can use the photoacid generator of enumerating in formula (1)～formula (68) in addition.
Formula (8)
Figure A20041005700400112
Formula (9)
Figure A20041005700400113
Formula (10)
Figure A20041005700400114
Figure A20041005700400115
Formula (13)
Figure A20041005700400117
Formula (15)
Formula (16)
Figure A200410057004001110
Formula (17)
Formula (18) Formula (19)
Formula (20)
Figure A20041005700400123
Formula (22) Formula (23)
Figure A20041005700400131
Figure A20041005700400132
Figure A20041005700400142
Formula (41)
Formula (42)
Figure A20041005700400151
Figure A20041005700400152
Figure A20041005700400161
Figure A20041005700400171
Figure A20041005700400173
Formula (63)
Figure A20041005700400174
Figure A20041005700400181
These photoacid generators can use separately, also can make up 2 kinds or its above use.In addition, its import volume is selected in the scope that with respect to 100 parts by weight resin (a-1) composition is 1～100 weight portion.If this amount less than 1 weight portion, then cross-linking reaction can not fully be carried out, and is difficult to obtain desirable resist pattern, if surpass 100 weight portions, then the storage stability variation of resist composition in addition.Therefore, the import volume of photoacid generator is preferably 1～100 weight portion with respect to 100 parts by weight resin (a-1) composition.
As Photobase generator, so long as directly or indirectly produce the i.e. qualification especially of material of alkali by rayed.Specifiable for example is, two [[(2-nitrobenzyl) oxygen] carbonyls oneself-1,6-diamines], cyclohexyl carbamic acid nitrobenzyl ester, 1, own diamino acid two (methoxy-benzyl) ester of 6-and with the compound of following formula (69)～formula (71) structure.
Figure A20041005700400191
Formula (69)
Figure A20041005700400192
Formula (70)
Formula (71)
Wherein in formula (69)～formula (71), R 1, R 2And R 3Expression hydrogen atom, replacement or unsubstituted alkyl and replacement or unsubstituted phenyl.
These Photobase generators and photoacid generator are same, can use separately, also can make up 2 kinds or its above use.In addition, based on above-mentioned same reason, its import volume is preferably 1～100 weight portion with respect to 100 parts by weight resin (a-1) composition.
Can be used for the optical free radical propellant (b-2) in the resin (a-2); specifiable is t-butyl peroxy isobutyrate for example; 2; 5-dimethyl-2; 5-two (benzoyl dioxy) hexane; 1; 4-two [α-(tert-butyl group dioxy)-isopropoxy] benzene; di-tert-butyl peroxide; 2; 5-dimethyl-2; 5-two (tert-butyl group dioxy) hexene hydroperoxides; α-(isopropyl phenyl)-isopropyl hydroperoxides; 2; the 5-dimethylhexane; tert butyl hydroperoxide; 1; 1-two (tert-butyl group dioxy)-3; 3; the 5-trimethyl-cyclohexane; butyl-4; 4-two (tert-butyl group dioxy) valerate; the cyclohexanone superoxide; 2; 2 '; 5; 5 '-four (t-butyl peroxy carbonyl) benzophenone; 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone; 3; 3 '; 4; 4 '-four (tertiary pentyl peroxide carbonyl) benzophenone; 3,3 ', 4; 4 '-four (uncle's hexyl peroxide carbonyl) benzophenone; 3; 3 '-two (t-butyl peroxy carbonyls)-4,4 '-benzophenonedicarboxylic acid; the t-butyl peroxy benzoic ether; organic peroxides such as di-t-butyl diperoxy isophthalic acid ester, 9; the 10-anthraquinone; the 1-chloroanthraquinone; the 2-chloroanthraquinone; the prestox anthraquinone; 1, quinones and benzoin methylethers such as 2-benzo anthraquinone; benzoin ethyl ether; the Alpha-Methyl benzoin; α-benzoin derivatives such as phenyl benzoin etc.
These optical free radical propellants can use separately, also can make up 2 kinds or its above use.In addition, based on above-mentioned same reason, its import volume is preferably 1～100 weight portion with respect to 100 parts by weight resin (a-2) composition.
As photosensitizer, can use present known photosensitizer.Specifiable is for example thioxanthene class, xanthene class, ketone, sulfo-pyrans salt, base phenylethylene, merocyanine class, 3-substituted cumarin class, 3,4-substituted cumarin class, cyanine class, acridine, thiazide, phenothiazines, anthracene class, coronene class, benzanthrene class, perylene kinds, merocyanine class, cumarin ketone, fumarine class, borate family.These can use separately, also can make up 2 kinds or its above use.
As the cross-linked compound (c-1) that can be used in the resin (a-1), be selected from least a kind of compound that forms crosslinked group in hydroxyl, hydroxyalkyl, the low-grade alkoxy alkyl so long as contain, promptly do not limit especially.
Specifiable for example is, contains the amino resins of hydroxyl or alkoxy, for example melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinamide-formaldehyde resin, ethylene urea-formaldehyde resin etc.
This cross-linked compound (c-1) can use for example amino hydrogen atom by melamine derivative, benzoguanamine derivant or the glycoluril of methylol or alkoxy methyl or both sides' replacement.This melamine derivative and benzoguanamine derivant can exist with dipolymer or trimeric form.These preferred per 1 triazine rings on average contain 3～6 methylols or alkoxy methyl.
Example as this melamine derivative or benzoguanamine derivant, specifiable is the MW-750 that per 1 triazine ring of commercially available product is on average replaced by 3.7 methoxies, MW-30 that per 1 triazine ring is on average replaced by 5.8 methoxies (more than be three and the manufacturing of ケ ミ カ Le) and サ イ メ Le 300,301,303,350,370,771,325,327,703,712 melamines such as methoxy such as grade, サ イ メ Le 235,236,238,212,253,254 melamines such as butoxymethyl such as methoxy such as grade, サ イ メ Le 506, butoxymethyl melamines such as 508, サ イ メ Le 1141 and so on contains the methoxy isobutoxy methylated melamines of carboxyl, サ イ メ Le 1123 and so on methoxy ethoxyl methyl benzoguanamine, サ イ メ Le 1123-10 and so on methoxy butoxymethyl benzoguanamine, サ イ メ Le 1128 and so on butoxymethyl benzoguanamine, サ イ メ Le 1125-80 and so on contains the methoxy ethoxyl methyl benzoguanamine (more than be the manufacturing of Mitsui サ イ テ Star Network) of carboxyl.In addition, specifiable as the example of glycoluril is サ イ メ Le 1170 and so on butoxymethyl glycoluril, サ イ メ Le 1172 and so on methylolation glycoluril etc.
In addition, contain the benzene or the phenol compound of hydroxyl or alkoxy, specifiable for example is, 1,3,5-three (methoxymethoxy) benzene, 1,2,4-three (isopropoxy methoxyl) benzene, 1,4-two (sec-butoxy methoxyl) benzene, 2,6-dihydroxymethyl-p-t-butyl phenol etc.
In addition, can use the compound that contains epoxy radicals, isocyanate group and have the crosslinked group of formation.Specifiablely as object lesson be, bisphenol acetone glycidol ether for example, novolac epoxy resin, cresol-novolac epoxy resin, isocyanuric acid triglycidyl group ester, the amino diphenylene of four glycidyl group, the four glycidyl group m-xylene diamine, four glycidyl group-1,3-two (amino-ethyl) cyclohexane, tetraphenyl glycidol ether ethane, triphenyl glycidol ether ethane, bis-phenol hexafluoro acetyl diglycidyl ether, 1, (1-(2 for 3-two, the 3-glycidoxy)-1-trifluoromethyl-2,2, the 2-trifluoromethyl) benzene, 4,4-two (2, the 3-glycidoxy) octafluoro biphenyl, the triglycidyl group para-aminophenol, the four glycidyl group m-xylene diamine, (4-(2 for 2-, the 3-glycidoxy) phenyl)-(4-(1 for 2-, (4-(2 for 1-two, the 3-glycidoxy) propane phenyl ethyl phenyl))), 1, (((4-(2 for 1-for 4-for 3-two, the 3-glycidoxy) phenyl)-1-(4-(1-(4-(2,3-glycidoxy phenyl)-1-Methylethyl) phenyl) ethyl) phenoxy group)-the 2-propyl alcohol etc.
These cross-linked compounds (c-1) can use separately, also can make up 2 kinds or its above use.In addition, its import volume is selected in the scope that with respect to 100 parts by weight resin (a-1) composition is 1～200 weight portion.If this amount less than 1 weight portion, then cross-linking reaction can not fully be carried out, and is difficult to obtain desirable resist pattern, if surpass 200 weight portions, then the storage stability variation of resist composition in addition.Therefore, the import volume of cross-linked compound is preferably 1～200 weight portion with respect to 100 parts by weight resin compositions.
As the cross-linked compound (c-2) that can be used in the resin (a-2), specifiable is the following compound that contains unsaturated group.Concrete specifiablely be, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloyl-oxy base oxethyl trimethylolpropane, poly-(methyl) acrylate equimolecular of glycerine polyglycidyl ether contains the compound of 3 polymerism unsaturated groups, also has ethylene glycol bisthioglycolate (methyl) acrylate, diglycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane bisphenol A-type two (methyl) acrylate, epoxypropane bisphenol A-type two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythrite two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, diglycol diglycidyl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate equimolecular contains the compound of 2 polymerism unsaturated groups, in addition also has (methyl) acrylic acid 2-hydroxyethyl ester, (methyl) acrylic acid 2-hydroxypropyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 2-phenoxy group-2-hydroxypropyl ester, 2-(methyl) acryloxy-2-hydroxypropyl phthalic ester, 3-chloro-2-hydroxypropyl (methyl) acrylate, glycerine list (methyl) acrylate, 2-(methyl) acryloxy ethyl phosphonic acid ester, N-methylol (methyl) acrylamide equimolecular contains the compound of 1 polymerism unsaturated group.
These cross-linked compounds can use separately, also can make up 2 kinds or its above use.In addition, its import volume is selected in the scope that with respect to 100 parts by weight resin (a-2) composition is 1～200 weight portion.If this amount less than 1 weight portion, then cross-linking reaction can not fully be carried out, and is difficult to obtain desirable resist pattern, if surpass 200 weight portions, then the storage stability variation of resist composition in addition.Therefore, the import volume of cross-linked compound is preferably 1～200 weight portion with respect to 100 parts by weight resin (a-2) composition.
Can be used for the resin (a-3) in the eurymeric resist composition, so long as the resin by heat curing, by the sour resolvent resin that produces by heat or rayed, polarity and molecular weight change, will show deliquescent resin to developer solution, the coating of exposed portion can be developed the resin that liquid is removed in this resin, does not promptly limit especially.
Resin (a-3) is specifiable to be, for example, contains the resin of hydroxyl or carboxyl etc.Concrete specifiable for example is, multipolymer, phenolics and the phenolic novolac of polyvinyl alcohol (PVA), polyacrylamide, polyacrylic acid, polymethylacrylic acid, polyamic acid, polycarboxylated styrene, polycarboxylated styrene derivant, polymethacrylate and maleic anhydride, the polyimide that contains hydroxyl and/or carboxyl, cellulose derivative, sugared skeleton macromolecular compound, polyamide, polyethylene terephthalate, polycarbonate, polyurethane and polysiloxane.More specifically specifiablely be the resin shown in the above-mentioned resin (a-1).These resins can separately or make up 2 kinds or its above use.
In addition, also can use the acrylic resin that contains carboxyl.Be principal ingredient promptly with (methyl) acrylate, copolymerization the acrylic copolymers that obtain of ethene unsaturated carboxylic acid and other monomer copolymerizations as required.Concrete specifiable is the resin shown in the above-mentioned resin (a-2).These resins can separately or make up 2 kinds or its above use.
Can be used for the photoacid generator (b-3) in the eurymeric resist composition, specifiable is naphthoquinone two azide.Generally can use 1,2-quinone diazide.Specifiable is for example 1,2-benzene quinone di-azide sulfonic acid ester, 1,2-naphthalene quinone di-azide sulfonic acid ester, 1,2-benzoquinones two nitrine sulfonic acid amides and 1,2-naphthoquinones two nitrine sulfonic acid amides etc.More specifically specifiable is 2,3,4-trihydroxybenzophenone-1,2-naphthoquinones nitrine-4-sulphonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,2 ', 4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,3 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,3 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4,2 ', 6-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,3,4,2 ', 6-pentahydroxybenzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,4,6,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, two (2, the 4-dihydroxy phenyl) methane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, two (2, the 4-dihydroxy phenyl) methane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, two (p-hydroxybenzene) methane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, two (p-hydroxybenzene) methane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, three (p-hydroxybenzene) methane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, three (p-hydroxybenzene) methane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 1,1,1-three (p-hydroxybenzene) ethane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 1,1,1-three (p-hydroxybenzene) ethane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) ethane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, two (2,3,4-trihydroxy phenyl) ethane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,2-two (2,3,4-trihydroxy phenyl) propane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,2-two (2,3,4-trihydroxy phenyl) propane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-and 3-phenyl-propane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-and 3-phenyl-propane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, two (2,5-dimethyl-4-hydroxy phenyl)-and 2-hydroxy phenyl methane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 3,3,3 ', 3 '-tetramethyl-1,1 '-spiral shell biindyl-5,6,7,5 ', 6 ', 7 '-six alcohol-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 3,3,3 ', 3 '-tetramethyl-1,1 '-spiral shell biindyl-5,6,7,5 ', 6 ', 7 '-six alcohol-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-naphthoquinones two nitrine-4-sulphonic acid ester, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane-1,2-naphthoquinones two nitrine-5-sulphonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinones two nitrine-4-sulfonic acid amides etc.
These naphthoquinone two azides can use separately, also can make up 2 kinds or its above use.In addition, its import volume is selected in the scope that with respect to 100 parts by weight resin (a-3) composition is 1～50 weight portion.If this amount less than 1 weight portion, then cross-linking reaction can not fully be carried out, and is difficult to obtain desirable resist pattern, if surpass 50 weight portions, then the storage stability variation of resist composition in addition.Therefore, the import volume of naphthoquinone two azide is preferably 1～50 weight portion with respect to 100 parts by weight resin compositions.
As the cross-linked compound (c-3) that can be used in the eurymeric resist composition, can use the compound that contains the crosslinked group of the formation that is selected from hydroxyl, hydroxy alkyl and the low-grade alkoxy alkyl at least a kind, perhaps contain epoxy radicals, isocyanate group and have the compound that forms crosslinked group, contain the compound of polymerism unsaturated group in addition.Concrete specifiable is shown in the above-mentioned negative resist composition (c-1).
These cross-linked compounds (c-3) can use separately, also can make up 2 or use more than its kind.In addition, its import volume is selected in the scope that with respect to 100 parts by weight resin (a-3) composition is 1～200 weight portion.If this amount less than 1 weight portion, then cross-linking reaction can not fully be carried out, and is difficult to obtain desirable resist pattern, if surpass 200 weight portions, then the storage stability variation of resist composition in addition.Therefore, the import volume of cross-linked compound is preferably 1～200 weight portion with respect to 100 parts by weight resin compositions.
Can be used for the dyestuff (d) in minus of the present invention and the eurymeric resist composition, can use to have as the desirable spectrophotometric spectra of color filter and directly be dissolved in the solvent or so that the form dissolved substances of dyestuff modification.As these dyestuffs, specifiable is acid dyes, oil-soluble dyes, disperse dyes, chemically-reactive dyes, direct dyes etc.Specifiable is for example azo dyes, benzoquinones class dyestuff, naphthoquinones class dyestuff, anthraquinone dyes, cyanine dye, square acids dyestuff (ス Network ア リ リ ウ system squarylium dye), Network ロ コ ニ ウ system class dyestuff, merocyanine class dyestuff, stilbene dye, diphenylmethyl alkanes dyestuff, triphenylmethane dye, Material of Fluoran dyestuff, spiro-pyrans class dyestuff, phthalocyanines dye, indigoid dye, ア Le ギ De class dyestuff, nickel complex class dyestuff and camomile lopps dyestuff.Concrete specifiable is the material of following Colour index number.C.I. solvent yellow 2,3,7,12,13,14,16,18,19,21,25,25:1,27,28,29,30,33,34,36,42,43,44,47,56,62,72,73,77,79,81,82,83,83:1,88,89,90,93,94,96,98,104,107,114,116,117,124,130,131,133,135,141,143,145,146,157,160:1,161,162,163,167,169,172,174,175,176,179,180,181,182,183,184,185,186,187,189,190,191, C.I. the solvent orange 1,2,3,4,5,7,11,14,20,23,25,31,40:1,41,45,54,56,58,60,62,63,70,75,77,80,81,86,99,102,103,105,106,107,108,109,110,111,112,113, C.I. solvent red 1,2,3,4,8,16,17,18,19,23,24,25,26,27,30,33,35,41,43,45,48,49,52,68,69,72,73,83:1,84:1,89,90,90:1,91,92,106,109,110,118,119,122,124,125,127,130,132,135,141,143,145,146,149,150,151,155,160,161,164,164:1,165,166,168,169,172,175,179,180,181,182,195,196,197,198,207,208,210,212,214,215,218,222,223,225,227,229,230,233,234,235,236,238,239,240,241,242,243,244,245,247,248, C.I. solvent violet 2,8,9,11,13,14,21,21:1,26,31,36,37,38,45,46,47,48,49,50,51,55,56,57,58,59,60,61, C.I. solvent blue 2,3,4,5,7,18,25,26,35,36,37,38,43,44,45,48,51,58,59,59:1,63,64,67,68,69,70,78,79,83,94,97,98,100,101,102,104,105,111,112,122,124,128,129,132,136,137,138,139,143, C.I. solvent green 1,3,4,5,7,28,29,32,33,34,35, C.I. solvent brown 1,3,4,5,12,20,22,28,38,41,42,43,44,52,53,59,60,61,62,63, C.I. solvent black 3,5,5:2,7,13,22,22:1,26,27,28,29,34,35,43,45,46,48,49,50, C.I. acid red 6,11,26,60,88,111,186,215, C.I. ACID GREEN 25,27, C.I. acid blue 22,25,40,78,92,113,129,167,230, C.I. Indian yellow 17,23,25,36,38,42,44,72,78, C.I. alkali red 1:1,2,13,14,22,27,29,39, C.I. Viride Nitens 3,4, C.I. alkali blue 3,9,41,66, C.I. alkaline purple 1,3,18,39,66, C.I. basic yellow 11,23,25,28,41, C.I. directly red 4,23,31,75,76,79,80,81,83,84,149,224, C.I. direct green 26,28, C.I. direct blue 71,78,98,106,108,192,201, C.I. direct purple 51, C.I. Direct Yellow 26,27,28,33,44,50,86,142, C.I. direct orange 26,29,34,37,72, C.I. sulphur red 5,6,7, C.I. sulphur green 2,3,6, C.I. sulphur indigo plant 2,3,7,9,13,15, C.I. the sulphur purple 2,3,4, C.I. Sulfur 4, C.I. urn red 13,21,23,28,29,48, C.I. urn green 3,5,8, C.I. vat blue 6,14,26,30, C.I. the urn purple 1,3,9,13,15,16, C.I. vat yellow 2,12,20,33, C.I. the urn orange 2,5,11,15,18,20, C.I. the azo coupling component 2,3,4,5,7,8,9,10,11,13,32,37,41,48, C.I. reactive red 8,22,46,120, C.I. reactive blue 1,2,7,19, C.I. reactive violet 2,4, C.I. reactive yellow 1,2,4,14,16, C.I. reactive orange 1,4,7,13,16,20, C.I. disperse red 4,11,54,55,58,65,73,127,129,141,196,210,229,354,356, C.I. disperse blue 3,24,79,82,87,106,125,165,183, C.I. disperse violet 1,6,12,26,27,28, C.I. disperse yellow 3,4,5,7,23,33,42,60,64, C.I. disperse orange 13,29,30.In order to express desirable spectrophotometric spectra, these dyestuffs can use separately, also can make up 2 kinds or its above use.
In containing the negative resist composition of dyestuff, the import volume of dyestuff (d) is selected in the scope that with respect to all solids composition of being made up of resin (a-1), photoacid generator or Photobase generator (b-1), cross-linked compound (c-1) and dyestuff (d) (100%) is 1～90 weight %.Under the few situation of the import volume of dyestuff, when the resist film filming, be difficult to the desirable spectrophotometric spectra of performance, under the many situations of the import volume of dyestuff, the storage stability variation of resist composition.Yet, in negative resist composition of the present invention, by using ketols solvent (e), the import volume of above-mentioned dyestuff (dye strength in the solid constituent) can use with the low concentration of counting weight % certainly, even be set at the high concentration of 30～90 weight %, also can fully guarantee the dissolubility of dyestuff.
In addition, in the negative resist composition of being made up of resin (a-2), optical free radical propellant (b-2), cross-linked compound (c-2) and dyestuff (d) that contains dyestuff, the import volume of dyestuff (d) is selected in the scope that with respect to all solids composition (100%) is 1～90 weight % equally.Under the few situation of the import volume of dyestuff, be difficult to the desirable spectrophotometric spectra of performance during the resist film filming, under the many situations of the import volume of dyestuff, the storage stability variation of resist composition.Yet, in negative resist composition of the present invention, by using ketols solvent (e), the import volume of above-mentioned dyestuff (dye strength in the solid constituent) can use with the low concentration of counting weight % certainly, even be set at the high concentration of 30～90 weight %, also can fully guarantee the dissolubility of dyestuff.
Also have, in containing the eurymeric resist composition of dyestuff, the import volume of dyestuff (d) is selected in the scope that with respect to all solids composition of being made up of resin (a-3), photoacid generator (b-3), cross-linked compound (c-3) and dyestuff (d) (100%) is 1～90 weight %.Under the few situation of the import volume of dyestuff, be difficult to the desirable spectrophotometric spectra of performance during the resist film filming, under the many situations of the import volume of dyestuff, the storage stability variation of resist composition.Yet, in negative resist composition of the present invention, by using ketols solvent (e), the import volume of above-mentioned dyestuff (dye strength in the solid constituent) can use with the low concentration of counting weight % certainly not to be had certainly, even be set at the high concentration of 30～90 weight %, also can fully guarantee the dissolubility of dyestuff.
The solvent (e) that can be used in minus of the present invention and the eurymeric resist composition is the ketols solvent.Wherein preferred beta-hydroxy ketone, specifiable as beta-hydroxy ketone is 4-hydroxy-4-methyl-2 pentanone, 4-hydroxy-4-methyl-methyl-n-butyl ketone, 4-hydroxyl-4-ethyl-methyl-n-butyl ketone, 4-hydroxy-4-methyl-2-heptanone, 4-hydroxyl-4-ethyl-2-heptanone, 4-hydroxyl-4-propyl group-2-heptanone, 2-methyl-2-hydroxyl-4-hexanone, 2-methyl-2-hydroxyl-4-pentanone, 2,3-dimethyl-3-hydroxyl-5-hexanone and 2,6-dimethyl-2-hydroxyl-4-heptanone etc.
Wherein from the dissolubility of so-called dyestuff and acquired aspect, most preferably 4-hydroxy-4-methyl-2 pentanone.
So-called keto-alcohol solvent among the present invention is meant and uses keto-alcohol, preferred beta-hydroxy ketone, preferred especially 4-hydroxy-4-methyl-2 pentanone (diacetone alcohol) basically separately, but also these keto-alcohols and other solvent can be used.From the dissolubility of raising dyestuff and the intermiscibility aspect of dyestuff and resin, when whole solvents are 100%, the import volume of keto-alcohol, preferred beta-hydroxy ketone, preferred especially 4-hydroxy-4-methyl-2 pentanone is 1～100 weight %, is preferably 10～100 weight %.
As other solvents that mix with keto-alcohol, specifiable is acetone for example, methyl alcohol, ethanol, isopropyl alcohol, the methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, the dipropylene glycol monomethyl ether, diglycol, the diglycol monotertiary acetic acid esters, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl butylacetic acid ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, Di Iso Propyl Ether, the ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, hexyl ether diox, N, the N-dimethyl acetamide, N, dinethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone, gamma-butyrolacton, normal hexane, n-pentane, normal octane, Anaesthetie Ether, cyclohexanone, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid propylene glycol list ethylether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid methyl esters, 3-ethoxy-c acid methyl ethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether etc.These keto-alcohols can be independent, also can make up 2 kinds or its above use.
In the minus and eurymeric resist composition that contains dyestuff of the present invention, containing of resin (a-1, a-2 or a-3), light trigger (b-1, b-2 or b-3), cross-linked compound (c-1, c-2 or c-3) and dyestuff (d) is proportional, be that solid component concentration is 5～50 weight %, be preferably 10～30 weight %.
This ratio is under the situation of less than 5 weight %, and the thickness of coating becomes too small, the problem of pin hole occurs producing.Surpassing under the situation of 50 weight % in addition, the viscosity of resist composition becomes excessive, thereby makes that the film thickness uniformity of coating is impaired.
For coating and the smooth voltinism that improves resist film, in the negative resist composition and eurymeric resist composition that contains dyestuff of the present invention, can contain surfactant.As such surfactant, specifiable is fluorine class surfactant, silicone based surfactant, nonionic class surfactant etc.
More specifically, specifiable is for example ェ Off ト Star プ EF301, EF303, EF352 (ト-ケ system プ ロ ダ Network Star is made), メ ガ Off ア Star Network F171, F173, R-30 (big Japanese イ Application キ makes), Off ロ ラ-De FC430, FC431 (Sumitomo ス リ-ェ system is made), ア サ ヒ ガ-De AG710, サ-Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass manufacturing) etc.The usage ratio of these surfactants is preferably 0.01～2 weight portion with respect to 100 parts by weight resin compositions, more preferably 0.01～1 weight portion.If the content of surfactant is greater than 2 weight portions, then resist film becomes inhomogeneous easily, if less than 0.01 weight portion then is easy to generate striped on resist film.
In addition, in order to improve the cohesive of develop back and substrate, can contain adhesion promotor.Object lesson as this adhesion promotor, specifiable is trimethyl chlorosilane for example, the dimethyl vinyl chlorosilane, methyldiphenyl base chlorosilane, chlorosilane classes such as CMDMCS chloromethyl dimethyl chlorosilane, the trimethyl methoxy silane, dimethyldiethoxysilane, methyl dimethoxysilane, dimethyl vinyl Ethoxysilane, dimethoxydiphenylsilane, alkoxyl silicone alkanes such as phenyl triethoxysilane, hexamethyldisilazane, N, N '-two (trimethyl silyl) urea, dimethyl trimethyl silyl amine, the silazane class of trimethyl-silyl-imidazole class, vinyl trichlorosilane, γ-r-chloropropyl trimethoxyl silane, γ-An Jibingjisanyiyangjiguiwan, γ-methacryloxypropyl trimethoxy silane, γ-silanes such as diglycidyl oxygen propyl trimethoxy silicane, benzotriazole, benzimidazole, indazole, imidazoles, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, the 2-mercaptobenzoxazole, urazole, the sulfo-uracil, mercaptoimidazole, heterogeneous ring compounds and 1 such as mercaptopyrimidine, 1-dimethylene urea, 1, the urea or the thiourea compound of 3-dimethyl urea etc.
The usage ratio of these adhesion promotors is with respect to 100 parts by weight resin compositions, is generally 20 weight portions or below it, preferred 0.05～10 weight portion, preferred especially 1～10 weight portion.
In the minus and eurymeric resist composition that contains dyestuff of the present invention, can also add with the resist composition has blended additive kind.Specifiable is for example to improve solvation mutually that sunproof ultraviolet light absorber and antioxidant, inhibition dyestuff separate out etc.As the object lesson that suppresses the phase solvation that dyestuff separates out, specifiable is polyoxyethylene Octyl Ether compound, the polyoxyethylene lauryl ether composition, polyxyethylated (carbon number 12～13) ether compound, secondary alkyl (carbon number 12～14) ether compound of polyoxyethylene, polyxyethylated (carbon number 13) ether compound, polyoxyethylene cetyl ether compound, polyoxyethylene stearyl base ether compound, the polyoxyethylene oleyl ether compound, polyoxyethylene decyl ethers compound, polyoxy alkylidene alkyl (carbon number 11～15) ether compound, secondary alkyl (carbon number 12～14) ether compound of polyoxy alkylidene, alkylether compounds such as polyoxy alkylidene cetyl ether compound, polyoxyethylene lauryl amino ethers compound, polyoxyethylene stearyl base amino ethers compound, alkyl amino ether compounds such as polyoxyethylene oil base amino ethers compound, polyoxyethylene lauric amide ether compound, polyoxyethylene 8 stearate amide ether compound, polyoxyethylene oleamide ether compound, the lauric acid diethyl amide compound, the Stearic acid diethanolamine salt compound, alkylamide ether compounds such as oleic acid diethyl amide compound, polyoxyethylene polystyrene-based phenyl ether compound, polyoxy alkylidene polystyrene-based phenyl ether compound, polyoxy alkylidene polystyrene-based phenyl ether formamide condensation product, polyoxyethylene list styryl phenyl ether compound, polyoxyethylene diphenylethyllene phenyl ether compound, aryl phenyl ether compounds such as polyoxyethylene naphthyl ether compound, the glyceryl monolaurate compound, the glyceryl monostearate compound, the glycerin mono-fatty acid ester compound, glycerine fatty acid ester compounds such as olein compound, the sorbitan monolaurate compound, sorbitan monopalmitate compound, the sorbitan monostearate compound, sorbitan tristearate compound, the dehydrated sorbitol mono-fatty acid ester compound, sorbitan ester compounds such as sorbitan trioleate compound, polyoxyethylene dilaurate compound, the polyoxyethylene laurate compound, the Myrj 45 compound, polyoxyethylene distearate compound, polyoxyethylene dioleate compound, fatty acid ether ester compounds such as polyoxyethylene oleate compound, the Emulsifier EL-60 ether compound, vegetable oil ether ester compounds such as polyoxyethylene hardened castor oil ether compound, polyoxyethylene sorbitan mono laurate ester compounds, polyoxyethylene sorbitan monostearate ester compounds, polyoxyethylene sorbitan monoleate compound, sorbitan ether ester compounds such as polyoxyethylene sorbitan trioleate compound, polyoxy alkylidene butyl ether compound, polyoxy alkylidene Octyl Ether compound, polyoxy alkylidene alkyl (carbon number 14～15) ether compound, one pure type polyether compounds such as polyoxy alkylidene oleyl ether compound, diol type polyether compounds such as polyoxyethylene polyoxypropylene condensation product, trimethylolpropane tris (polyoxy alkylidene) ether compound, polyvalent alcohol type polyether compounds such as polyoxy alkylidene glycerin ether compound, the methyl laurate compound, the methyl oleate compound, the isopropyl myristate compound, the butyl stearate compound, the octyl palmitate compound, the octyl stearate compound, oleic acid Lauryl Ester compound, stearic acid isotridecyl ester compounds, the oleyl oleate compound, hexane diacid two grease compounds, trimethylolpropane tris decylate compound, the trimethylolpropane trilaurate compound, pentaerythrite dioleate compound, pentaerythrite monostearate ester compounds, fatty acid alkyl ester compounds such as pentaerythritol stearic acid ester 2 compound, the alkyl sulfonic acid ester compounds, the long-chain alkyl benzene sulfoacid compound, the branched alkylbenzene sulfoacid compound, the long-chain alkyl benzene sulfonate compound, the branched alkylbenzene sulfonate compound, branched alkyl diphenyl ether disulfonate compound, naphthalene sulfonic acids one isopropyl esters compound, naphthalene sulfonic acids diisopropyl ester compounds, naphthalene sulfonic acids triisopropyl ester compounds, naphthalene sulfonic acids dibutyl ester compounds, sulfonic acid type compounds such as sulfosuccinic acid dioctyl ester compounds, oleic acid sulfated oil compound, castor oil sulphation compound, sulfuric acid monooctyl ester compound, the lauryl sulfate compound, the alkyl sodium sulfate ester compounds, sulfate compounds such as alkyl ether sulphate compound, cellulose, cellulose derivative, sugar skeleton macromolecular compound.
The usage ratio of these phase solvations is 0.001～20 weight portion with respect to 100 parts by weight resin compositions.The situation that the few situation of use amount and use amount are many is compared, and the inhibition of separating out of dyestuff can variation, is difficult to obtain good pattern form under the situation mostly.But do not damage at the phase solvation under the situation of pattern form, can use more than 20 weight portions.
Below the method that negative resist composition that contains dyestuff that color filter of the present invention uses and eurymeric resist composition are made color filter is used in explanation.
Employing spin-coating methods etc. are coated in negative resist composition and the eurymeric resist composition that contains dyestuff of the present invention on silicon wafer or the glass substrate to obtain the revolution of desirable resist thickness, carry out gentleness baking (burning till).As long as gentle baking makes solvent evaporation, preferably in 50～150 ℃ temperature range, carried out 30 seconds～10 minutes.By mask, be 100～2000mJ/cm then in exposure 2About down exposure.Exposure can be used for example ultraviolet ray, far ultraviolet, electronics line or X ray etc. such as mercury vapor lamp.The exposure back forms under the situation of minus pattern at the negative resist composition that use contains dyestuff, preferably heats (PEB (postexposure bake)).Acid that produces by PEB, by exposure or alkali further carry out crosslinked, further enlarge the poor solubility of unexposed portion with respect to developer solution, improve contrast.PEB preferably carried out in 50～150 ℃ temperature range 30 seconds～5 minutes.
Then develop.As not restriction especially of developing method, can be undertaken by known method such as oar formula paddling process, infusion process, spray process.Development temperature is preferably between 20 ℃～30 ℃, and preferred dipping is 10 seconds～10 minutes in developer solution.
As developer solution, can be with an organic solvent or alkaline aqueous solution etc.Concrete specifiable is isopropyl alcohol, propylene glycol monomethyl ether, ethylamine solution, n-propylamine aqueous solution, diethylamine aqueous solution, di-n-propylamine aqueous solution, triethylamine aqueous solution, methyl-diethyl-amine aqueous solution, diethanolamine aqueous solution, triethanolamine aqueous solution, tetramethylammonium hydroxide aqueous solution, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, sodium silicate aqueous solution, sodium metasilicate aqueous solution etc.
Also have,, preferably add surfactant in order to improve the removal of unexposed portion in the developer solution.As object lesson, specifiable is polyoxyethylene Octyl Ether compound, the polyoxyethylene lauryl ether compound, polyxyethylated (carbon number 12～13) ether compound, secondary alkyl (carbon number 12～14) ether compound of polyoxyethylene, polyxyethylated (carbon number 13) ether compound, polyoxyethylene cetyl ether compound, polyoxyethylene stearyl base ether compound, the polyoxyl 10 oleyl ether compound, polyoxyethylene decyl ethers compound, polyoxy alkylidene alkyl (carbon number 11～15) ether compound, secondary alkyl (carbon number 12～14) ether compound of polyoxy alkylidene, alkylether compounds such as polyoxy alkylidene cetyl ether compound, polyoxyethylene lauryl amino ethers compound, polyoxyethylene stearyl base amino ethers compound, alkyl amino ether compounds such as polyoxyethylene oil base amino ethers compound, polyoxyethylene lauric amide ether compound, polyoxyethylene 8 stearate amide ether compound, polyoxyethylene oleamide ether compound, the lauric acid diethyl amide compound, the Stearic acid diethanolamine salt compound, alkylamide ether compounds such as oleic acid diethyl amide compound, polyoxyethylene polystyrene-based phenyl ether compound, polyoxy alkylidene polystyrene-based phenyl ether compound, polyoxy alkylidene polystyrene-based phenyl ether formamide condensation product, polyoxyethylene one styryl phenyl ether compound, polyoxyethylene diphenylethyllene phenyl ether compound, aryl phenyl ether compounds such as polyoxyethylene naphthyl ether compound, the glyceryl monolaurate compound, the glyceryl monostearate compound, the glycerin mono-fatty acid ester compound, glycerine fatty acid ester compounds such as olein compound, the sorbitan monolaurate compound, sorbitan monopalmitate compound, the sorbitan monostearate compound, sorbitan tristearate compound, the dehydrated sorbitol mono-fatty acid ester compound, sorbitan ester compounds such as sorbitan trioleate compound, polyoxyethylene dilaurate compound, the polyoxyethylene laurate compound, the Myrj 45 compound, polyoxyethylene distearate compound, polyoxyethylene dioleate compound, fatty acid ether ester compounds such as polyoxyethylene oleate compound, the Emulsifier EL-60 ether compound, vegetable oil ether ester compounds such as polyoxyethylene hardened castor oil ether compound, polyoxyethylene sorbitan mono laurate ester compounds, polyoxyethylene sorbitan monostearate ester compounds, polyoxyethylene sorbitan monoleate compound, sorbitan ether ester compounds such as polyoxyethylene sorbitan trioleate compound, polyoxy alkylidene butyl ether compound, polyoxy alkylidene Octyl Ether compound, polyoxy alkylidene alkyl (carbon number 14～15) ether compound, one pure type polyether compounds such as polyoxy alkylidene oleyl ether compound, diol type polyether compounds such as polyoxyethylene polyoxypropylene condensation product, trimethylolpropane tris (polyoxy alkylidene) ether compound, polyvalent alcohol type polyether compounds such as polyoxy alkylidene glycerin ether compound, the methyl laurate compound, the methyl oleate compound, the isopropyl myristate compound, the butyl stearate compound, the octyl palmitate compound, the octyl stearate compound, oleic acid Lauryl Ester compound, stearic acid isotridecyl ester compounds, the oleyl oleate compound, hexane diacid two grease compounds, trimethylolpropane tris decylate compound, the trimethylolpropane trilaurate compound, pentaerythrite dioleate compound, the pentaerythritol monostearate compound, fatty acid alkyl ester compounds such as pentaerythritol stearic acid ester 2 compound, the alkyl sulfonic acid ester compounds, the long-chain alkyl benzene sulfoacid compound, the branched alkylbenzene sulfoacid compound, the long-chain alkyl benzene sulfonate compound, the branched alkylbenzene sulfonate compound, branched alkyl diphenyl ether disulfonate compound, naphthalene sulfonic acids list isopropyl esters compound, naphthalene sulfonic acids diisopropyl ester compounds, naphthalene sulfonic acids triisopropyl ester compounds, naphthalene sulfonic acids dibutyl ester compounds, sulfonic acid type compounds such as sulfosuccinic acid dioctyl ester compounds, oleic acid sulfated oil compound, castor oil sulphation compound, sulfuric acid monooctyl ester compound, the lauryl sulfate compound, the alkyl sodium sulfate ester compounds, sulfate compounds such as alkyl ether sulphate compound.The preferred concentration of alkaline-based developer is that alkaline components is 0.001～10 weight %, and surfactant component is 0.001～10 weight %.Development capability is strong excessively if alkaline components is too high, soaks into to exposed portion when soaking into to unexposed portion, eurymeric when minus, causes that easily patterned surfaces is coarse, if mistake is hanged down then can not be obtained development capability.In addition, it is inhomogeneous to bubble easily and take place easily to develop if surfactant component is too high, if cross low then can not obtain development capability.
After the development, preferably adopt water or common organic solvents drip washing.Then by the dry pattern that forms.Contain in use under the situation of negative resist composition of dyestuff, form that exposed portion solidifies, the minus pattern of unexposed portion dissolving, contain in use under the situation of eurymeric resist composition of dyestuff, form the eurymeric pattern of exposed portion dissolving.
By replacing shades of colour and mask, repeating above a series of operation, can obtain making up the colored pattern of required pigment according to required number of times.In addition after pattern forms, for make remaining in the pattern can polymerization or functional group's complete reaction of condensation, also can heat (back baking).The back baking both can be carried out behind the versicolor pattern of each formation, also can carry out after all forming colored pattern, preferably carried out in 150～500 ℃ temperature range 30 minutes～2 hours.
[embodiment]
(containing the modulation of the negative resist composition of dyestuff)
Phenolic novolac: the phenolic novolac A that phenol and formaldehyde condensation obtain (number-average molecular weight 9000 (polystyrene conversion))
Polyhydroxystyrene resin: VP8000 (Japanese Cao Da makes)
Polycarboxylated styrene multipolymer: マ Le カ-リ Application カ-CHM (to the multipolymer of vinylphenol and methacrylic acid 2-hydroxyl ethyl ester, mol ratio is 1: 1) (ball is apt to the oil manufacturing)
Acrylic resin: the acryl resin A (multipolymer of (methyl) acrylic acid, (methyl) hydroxy-ethyl acrylate and (methyl) methyl acrylate, mol ratio is 9: 25.5: 65.5 a propylene glycol monomethyl ether acetate solution, solid component concentration: 22.0 weight %, weight-average molecular weight 6000 (polystyrene conversion))
Embodiment 1
In the 50ml eggplant type flask, add 1.76g as phenolic novolac A, the 1.10g of line style Novolac resin ValifastRed1355 (オ リ ェ Application ト chemistry is made), 9.43g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stir as the pink group dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.18g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303, Mitsui サ イ テ Star Network are made) of cross-linked compound, 0.09g triazines photoacid generator (trade name TAZ-108 as photoacid generator, the manufacturing of body ど り chemistry), 0.009g is as fluorine class surfactant (the trade name メ ガ Off ア Star Network R-30 of surfactant, big Japanese イ Application キ chemistry is made), at room temperature stir again, obtain containing the negative resist composition (1) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.Use the part of the negative resist composition (1) that contains dyestuff that the filtrator of 0.2 μ m will obtain to filter, placed for 1 week under room temperature in the sample plasma bottle of cleaning, visual observations is not found foreign matter.
Embodiment 2
In the 50ml eggplant type flask, add 1.76g as phenolic novolac A, the 1.10g of phenolic novolac ValifastRed1355,9.43g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stir as the pink group dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.35g as the butoxymethyl glycoluril class cross-linked compound (trade name サ イ メ Le 1170, Network manufacturing) of cross-linked compound, 0.18g sulfonic acid esters photoacid generator (trade name N Mitsui サ イ テ Star Network AI-105 as photoacid generator, the manufacturing of body ど り chemistry), 0.012g is as the fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) of surfactant, at room temperature stir again, obtain containing the negative resist composition (2) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (2) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 3
In the 50ml eggplant type flask, add 1.76g as phenolic novolac A, the 1.10g of phenolic novolac ValifastRed1355,9.43g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stir as the pink group dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.25g as the epoxies cross-linked compound (trade name GT-401, ダ イ セ Le chemistry are made) of cross-linked compound, 0.12g sulfonium salt type photoacid generator (trade name DTS-105 as photoacid generator, the manufacturing of body ど り chemistry), 0.010g is as the fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) of surfactant, at room temperature stir again, obtain containing the negative resist composition (3) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (3) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 4
In the 50ml eggplant type flask, add 1.00g as phenolic novolac A, the 2.00g of phenolic novolac ValifastRed1355,4.14g solvent 4-hydroxy-4-methyl-2 pentanone and 6.21g propylene glycol monomethyl ether, at room temperature stir as the pink group dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.30g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.15g triazines photoacid generator (trade name TAZ-107 as photoacid generator, the manufacturing of body ど り chemistry), 0.009g is as the fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) of surfactant, at room temperature stir again, obtain containing the negative resist composition (4) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (4) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 5
In the 50ml eggplant type flask, add 1.00g as phenolic novolac A, the 2.00g of phenolic novolac ValifastRed1355,3.11g solvent 4-hydroxy-4-methyl-2 pentanone and 7.25g ethyl lactate, at room temperature stir as the pink group dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.15g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.07g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (5) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (5) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 6
In the 100ml eggplant type flask, add 7.07g as acryl resin A, the 0.27g of acrylic resin as the RedGS of pink group dyestuff (day become to change into manufacturings), 36.80g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stirring.Do not see insolubles in the reaction solution, be uniform solution.Then, add 3.31g cross-linked compound (trade name KAYARADDPHA-40H, Japanese chemical drug manufacturing), 0.30g optical free radical propellant (trade name I-369, チ バ ス ペ シ ヤ リ テ イ-ケ ミ カ Le ズ makes), 0.20g photosensitizer (trade name ITX, Off ア-ス ト ケ ミ カ Le コ-Port レ-シ ヨ Application is made), 0.015g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (6) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (6) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 7
In the 50ml eggplant type flask, add 1.00g as phenolic novolac A, the 2.00g of phenolic novolac SavinylFireRedGLS (Network ラ リ ア Application ト manufacturings), 10.35g solvent 4-hydroxy-4-methyl-2 pentanone, stirring at room temperature as the pink group dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.30g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.15g as the triazines photoacid generator (trade name TAZ-107) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (7) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (7) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 8
In the 50ml eggplant type flask, add 1.00g as phenolic novolac A, the 5.80g of phenolic novolac SavinylFireRedGLS, 13.51g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stir as the pink group dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.40g as the methoxy cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.18g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.01g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (8) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (8) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 9
In the 50ml eggplant type flask, add 1.76g as VP8000, the 1.10g of polycarboxylated styrene ValifastGreen1501 (オ リ ェ Application ト chemistry is made), 9.43g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stir as green class dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.18g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.09g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (9) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (9) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 10
In the 50ml eggplant type flask, add 1.00g as VP8000, the 2.00g of polycarboxylated styrene ValifastGreen1501,4.14g solvent 4-hydroxy-4-methyl-2 pentanone and 6.21g propylene glycol methyl ether acetate, at room temperature stir as green class dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.50g as the methoxy melamine compound (trade name サ イ メ Le 303) of cross-linked compound, 0.25g as the triazines photoacid generator (trade name TAZ-107) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (10) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (10) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 11
In the 50ml eggplant type flask, add 1.76g as マ Le カ-リ Application カ-CHM, the 1.10g of polycarboxylated styrene multipolymer ValifastBlue1621 (オ リ エ Application ト chemistry is made), 9.43g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stir as blue class dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.18g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.09g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (11) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (11) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 12
In the 50ml eggplant type flask, add 1.00g as マ Le カ-リ Application カ-CHM, the 5.80g of polycarboxylated styrene multipolymer ValifastBlue1621,13.51g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stir as blue class dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.50g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.20g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.01g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (12) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (12) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 13
In the 50ml eggplant type flask, add 1.00g as マ Le カ-リ Application カ-CHM, the 2.00g of polycarboxylated styrene multipolymer ValifastBlue2620 (オ リ ェ Application ト chemistry is made), 10.35g solvent 4-hydroxy-4-methyl-2 pentanone, at room temperature stir as blue class dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.30g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.15g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.012g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (13) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (13) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Embodiment 14
In the 50ml eggplant type flask, add 1.00g as マ Le カ-リ Application カ-CHM, the 2.00g of polycarboxylated styrene multipolymer ValifastBlue2620,4.14g solvent 4-hydroxy-4-methyl-2 pentanone and 6.21g propylene glycol monomethyl ether, at room temperature stir as blue class dyestuff.Do not see insolubles in the reaction solution, be uniform solution.Then, add 0.30g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.15g as the triazines photoacid generator (trade name TAZ-107) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, obtain containing the negative resist composition (14) of dyestuff.Do not see insolubles in the solution, obtain uniform solution.The negative resist composition (14) that a part of using the filtrator of 0.2 μ m to obtain contains dyestuff filters, and places for 1 week under room temperature in the sample plasma bottle of cleaning, and visual observations is not found foreign matter.
Comparative example 1
In the 50ml eggplant type flask, add 1.76g as phenolic novolac A, the 1.10g of phenolic novolac ValifastRed1355,9.43g solvent propylene glycol monomethyl ether, separate out dyestuff when at room temperature stirring in the reaction solution as the pink group dyestuff.Then, add 0.18g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.09g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30 as surfactant,), at room temperature stir again, but dyestuff does not dissolve, and does not obtain uniform solution.In addition, during the dyestuff of in the negative resist composition (15) that contains inhomogeneous dyestuff that filtration obtains, separating out, obtain the 0.54g dyestuff.The result can not obtain to contain the negative resist composition of the dyestuff of regulation dye strength.The filtrator that re-uses 0.2 μ m will filter according to the negative resist composition (15) that contains inhomogeneous dyestuff that same modulator approach obtains, and when placing in the sample plasma bottle of cleaning, range estimation in the 1st day is observed and do not found foreign matter.
Comparative example 2
In the 50ml eggplant type flask, add 1.76g as VP8000, the 1.10g of polycarboxylated styrene ValifastGreen1501,9.43g solvent propylene glycol monomethyl ether, separate out dyestuff when at room temperature stirring in the reaction solution as green class dyestuff.Then, add 0.18g as the methoxy melamine compounds (trade name サ イ メ Le 303) of cross-linked compound, 0.09g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, but dyestuff does not dissolve, and does not obtain uniform solution.In addition, during the dyestuff of in the negative resist composition (16) that contains inhomogeneous dyestuff that filtration obtains, separating out, obtain the 0.46g dyestuff.The result can not obtain to contain the negative resist composition of the dyestuff of regulation dye strength.The filtrator that re-uses 0.2 μ m will filter according to the negative resist composition (16) that contains inhomogeneous dyestuff that same modulator approach obtains, and when placing in the sample plasma bottle of cleaning, range estimation in the 1st day is observed and do not found that foreign matter produces.
Comparative example 3
In the 50ml eggplant type flask, add 1.76g as マ Le カ-リ Application カ-CHM, the 1.10g of polycarboxylated styrene multipolymer ValifastBlue1621,9.43g solvent ethyl lactate, separate out dyestuff when at room temperature stirring in the reaction solution as blue class dyestuff.Then, add 0.18g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.09g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.006g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, but dyestuff does not dissolve, and does not obtain uniform solution.In addition, during the dyestuff of in the negative resist composition (17) that contains inhomogeneous dyestuff that filtration obtains, separating out, obtain the 0.55g dyestuff.The result can not obtain to contain the negative resist composition of the dyestuff of regulation dye strength.The filtrator that re-uses 0.2 μ m will filter according to the negative resist composition (17) that contains inhomogeneous dyestuff that same modulator approach obtains, and when placing under room temperature in the sample plasma bottle of cleaning, range estimation in the 1st day is observed and do not found that foreign matter produces.
Comparative example 4
In the 50ml eggplant type flask, add 1.76g as マ Le カ-リ Application カ-CHM, the 1.10g of polycarboxylated styrene multipolymer ValifastBlue1621,4.72g solvent propylene glycol monomethyl ether and 4.72g propylene glycol methyl ether acetate, separate out dyestuff when at room temperature stirring in the reaction solution as blue class dyestuff.Then, add 0.18g as the methoxy melamine class cross-linked compound (trade name サ イ メ Le 303) of cross-linked compound, 0.09g as the triazines photoacid generator (trade name TAZ-108) of photoacid generator, 0.009g fluorine class surfactant (trade name メ ガ Off ア Star Network R-30) as surfactant, at room temperature stir again, but dyestuff does not dissolve, and does not obtain uniform solution.In addition, during the dyestuff of in the negative resist composition (18) that contains inhomogeneous dyestuff that filtration obtains, separating out, obtain the 0.65g dyestuff.The result can not obtain to contain the negative resist composition of the dyestuff of regulation dye strength.The filtrator that re-uses 0.2 μ m will filter according to the negative resist composition (18) that contains inhomogeneous dyestuff that same modulator approach obtains, and when placing under room temperature in the sample plasma bottle of cleaning, range estimation in the 1st day is observed and do not found that foreign matter produces.
(making of color filter)
The silicon wafer sizes that embodiment 15 to embodiment 28 and comparative example 5 use to the comparative example 8 is identical.
Also have, have or not on the patterned coatings that forms on observing silicon wafer when having foreign matter, the visual observations of using sodium vapor lamp is by observing the affirmation of carrying out foreign matter in the position of darkroom middle distance silicon wafer one side 30cm.If can confirm foreign matter, add up to the sum of seeing on the silicon wafer.In addition, use the observation of optical microscope to adopt 1000 times of multiplying powers to carry out,, then measure its size if can confirm foreign matter.
Embodiment 15
Use the filtrator of 0.2 μ m that the negative resist composition (1) that contains dyestuff that obtains among the embodiment 1 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.95 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), exposure is 300mJ/cm among the irradiation 365nm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Pattern does not take place form the pattern of the resolution of pattern until line/interval 2 μ m with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 16
Use the filtrator of 0.2 μ m that the negative resist composition (2) that contains dyestuff that obtains among the embodiment 2 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 1.00 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), exposure is 300mJ/cm among the irradiation 365nm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Do not have pattern to form pattern is line/interval 5 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 17
Use the filtrator of 0.2 μ m that the negative resist composition (3) that contains dyestuff that obtains among the embodiment 3 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.98 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Do not have pattern to form pattern is line/interval 5 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 18
Use the filtrator of 0.2 μ m that the negative resist composition (4) that contains dyestuff that obtains among the embodiment 4 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.96 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 19
Use the filtrator of 0.2 μ m that the negative resist composition (5) that contains dyestuff that obtains among the embodiment 5 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 1.03 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 20
Use the filtrator of 0.2 μ m that the negative resist composition (6) that contains dyestuff that obtains among the embodiment 6 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 1.05 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Do not have pattern to form pattern is line/interval 10 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 21
Use the filtrator of 0.2 μ m that the negative resist composition (7) that contains dyestuff that obtains among the embodiment 7 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 1.00 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 500mJ/cm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 22
Use the filtrator of 0.2 μ m that the negative resist composition (8) that contains dyestuff that obtains among the embodiment 8 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.94 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 23
Use the filtrator of 0.2 μ m that the negative resist composition (9) that contains dyestuff that obtains among the embodiment 9 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 1.10 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form green minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 24
Use the filtrator of 0.2 μ m that the negative resist composition (10) that contains dyestuff that obtains among the embodiment 10 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.98 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 120 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form green minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 25
Use the filtrator of 0.2 μ m that the negative resist composition (11) that contains dyestuff that obtains among the embodiment 11 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 1.00 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 130 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form blue minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 26
Use the filtrator of 0.2 μ m that the negative resist composition (12) that contains dyestuff that obtains among the embodiment 12 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.94 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 130 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form blue minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 27
Use the filtrator of 0.2 μ m that the negative resist composition (13) that contains dyestuff that obtains among the embodiment 13 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.94 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 130 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form blue minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Embodiment 28
Use the filtrator of 0.2 μ m that the negative resist composition (14) that contains dyestuff that obtains among the embodiment 14 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.95 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 130 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form blue minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.On the patterned coatings that forms on the silicon wafer, do not find foreign matter when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, do not find foreign matter in addition yet.
Comparative example 5
Use the filtrator of 0.2 μ m that the negative resist composition (15) that contains dyestuff that obtains in the comparative example 1 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 1.04 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 130 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form red minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.Yet on the patterned coatings that forms on the silicon wafer, find the foreign matter more than 50 when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, find the foreign matter of 2～3 μ m sizes in addition.
Comparative example 6
Use the filtrator of 0.2 μ m that the negative resist composition (16) that contains dyestuff that obtains in the comparative example 2 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 1.00 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 130 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form green minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.Yet on the patterned coatings that forms on the silicon wafer, find the foreign matter more than 50 when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, find the foreign matter of 2～4 μ m sizes in addition.
Comparative example 7
Use the filtrator of 0.2 μ m that the negative resist composition (17) that contains dyestuff that obtains in the comparative example 4 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on silicon wafer then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.94 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 130 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form blue minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.Yet on the patterned coatings that forms on the silicon wafer, find the foreign matter more than 50 when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, find the foreign matter of 2～4 μ m sizes in addition.
Comparative example 8
Use the filtrator of 0.2 μ m that the negative resist composition (18) that contains dyestuff that obtains in the comparative example 5 is filtered, in the sample plasma bottle of cleaning, under room temperature, placed 2.Use spinner application composition on prosperous of silicon then, gentle baking (burning till) is 1 minute on 100 ℃ electric hot plate, forms the coating of 0.99 μ m thickness.By test mask, by xenon system ultraviolet lamp PLA-501 (F), the exposure of irradiation 365nm is 300mJ/cm on this coating 2Ultraviolet ray.Then on 130 ℃ electric hot plate, carry out 1 minute PEB.Then, the dipping certain hour develops in 23 ℃ NMD-3 developer solutions (manufacturing should be changed in Tokyo), carries out flowing water with pure water again and cleans.On 150 ℃ electric hot plate, carry out 5 minutes back baking then, form blue minus pattern.Do not have pattern to form pattern is line/interval 2 μ m until the resolution of pattern with peeling off.Yet on the patterned coatings that forms on the silicon wafer, find the foreign matter more than 50 when under sodium vapor lamp, carrying out visual observations.When carrying out observation by light microscope, find the foreign matter of 2～4 μ m sizes in addition.

Claims (12)

1. the resist composition that contains dyestuff that contains the ketols solvent.
2. the negative resist composition that contains resin (a-1), photoacid generator or Photobase generator (b-1), cross-linked compound (c-1), dyestuff (d) and ketols solvent (e).
3. the negative resist composition that contains resin (a-2), optical free radical propellant (b-2), cross-linked compound (c-2), dyestuff (d) and ketols solvent (e).
4. the eurymeric resist composition that contains resin (a-3), photoacid generator (b-3), cross-linked compound (c-3), dyestuff (d) and ketols solvent (e).
5. the resist composition of record in any 1 of the claim 1 to 4, wherein solvent contains the keto-alcohol with respect to whole solvent at least 1 weight %.
6. the resist composition of record in any 1 of the claim 1 to 5, wherein keto-alcohol is a beta-hydroxy ketone.
7. the resist composition of record in any 1 of the claim 1 to 5, wherein keto-alcohol is 4-hydroxy-4-methyl-2 pentanone.
8. manufacturing method of color filter comprises that resist composition with record in any 1 of the claim 1 to 7 is coated on the substrate, dry, operation that exposure is developed then.
9. adopt the color filter of the method manufacturing of record in the claim 8.
10. the solid-state imager that contains the color filter of the method manufacturing of adopting record in the claim 8.
11. contain the liquid crystal display cells of the color filter of the method manufacturing of adopting record in the claim 8.
12. contain the diode displaying element of the color filter of the method manufacturing of adopting record in the claim 8.
CN200410057004XA 2003-08-21 2004-08-20 Dye-containing resist composition and color filter using same Expired - Fee Related CN1584631B (en)

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